WO2012148360A1 - Membranes en polymère/copolymère de cardo-polybenzoxazole pour une perméabilité améliorée et son procédé de fabrication - Google Patents

Membranes en polymère/copolymère de cardo-polybenzoxazole pour une perméabilité améliorée et son procédé de fabrication Download PDF

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WO2012148360A1
WO2012148360A1 PCT/SG2012/000153 SG2012000153W WO2012148360A1 WO 2012148360 A1 WO2012148360 A1 WO 2012148360A1 SG 2012000153 W SG2012000153 W SG 2012000153W WO 2012148360 A1 WO2012148360 A1 WO 2012148360A1
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cardo
integer
polybenzoxazole
copolymer
membrane
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Yin Fong YEONG
Huan Wang
Tai-Shung Neal Chung
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National University of Singapore
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B01D69/088—Co-extrusion; Co-spinning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/22—Specific non-solvents or non-solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain

Definitions

  • Membrane-based technology has emerged as an economical and highly energy-efficient alternative to conventional technology in separation applications.
  • Polymeric membranes in particular, are advantageous due to their low cost, good permeability, mechanical stability, ease of fabrication, and scalability of the fabrication process [1-3].
  • the molecular structure of the polymeric membrane correlates to the permeability and permselectivity of the membrane [4-5].
  • Polyimide (PI) polymer membranes have been applied to gas separation processes with limited success.
  • Polyimides are composed of rigid main chains with strong intermolecular interactions, which results in small polymer size, and low fractional free volume [7-8].
  • PBO Polybenzoxazole
  • These membranes which may be generated via a thermal rearrangement of PI membranes [12], exhibit excellent thermal and chemical stability as well as enhanced permselectivity.
  • the rigid ring units of PBO enable efficient packing of the polymer, which results in lower fractional free volume, and therefore lower gas permeability through a polybenzoxazole membrane.
  • a cardo-polybenzoxazole copolymer having the structure of formula (I):
  • m is an integer from 0 to 100;
  • n is an integer from 0 to 100;
  • p is an integer from 0 to 1 ;
  • R and R are independently (Ci-C 6 )alkyl or (C[-C6)haloalkyl;
  • A is either a methylene linker of the formula CR"R" or a polycyclic aromatic hydrocarbon such that when A is not present, there is a fused ring system, and when A is present, there is a multi-ring system;
  • R 3 and R 4 are independently (Ci-C 6 )alkyl or (C6-C 2 4)aryl, or R 3 and R 4 can be taken together to form a cardo group;
  • R 5 and R 6 are independently (C l -C 6 )alkyl or (C i -C 6 )haloalkyl .
  • a and b are each integers independently selected from zero to 5 and the sum of a and b is less than or equal to 10;
  • q is an integer from zero to 1 ;
  • each R 7 is independently selected from H, (Ci-C 6 )alkyl, (C6-C 24 )aryl, or heteroaryl;
  • p is an integer from 1 to 4.
  • the cardo-polybenzoxazole copolymer of the present invention comprises units of both cardo-polybenzoxazole and polybenzoxazole.
  • the cardo-polybenzoxazole copolymer comprises repeating units of formula (III):
  • m is an integer trom U to 1UU;
  • n is an integer from 0 to 100;
  • the cardo-polybenzoxazole copolymer of the invention is in the form of a membrane having a geometry comprising flat sheet, hollow fiber, tube, thin film composite, or disk.
  • the process of forming a cardo-polybenzoxazole copolymer membrane comprises a) synthesizing a cardo-copolyimide material by polycondensation of a diphthalic anhydride with a mixture of diamine and cardo-diamine; b) casting a solution of the cardo-copolyimide into a membrane; and c) exposing the membrane of step b) to a temperature and pressure that will bring about a thermal
  • cardo-copolyimide membrane rearrangement of the cardo-copolyimide membrane to form a cardo- polybenzoxazole copolymer membrane.
  • the cardo-polybenzoxazole membranes of the invention can be fabricated into geometries including, but not limited to, flat sheet, hollow fiber, tube, thin film, and disk.
  • the present invention also discloses a method for the separation of a fluid from a mixture of fluids.
  • the process for separating at least one fluid from a mixture of fluids comprises: a) providing a cardo-polybenzoxazole copolymer membrane; and b) bringing a mixture of fluids under pressure into contact with the membrane of step a), whereby one of the at least one fluids permeates the membrane preferentially with respect to at least one other fluid in the mixture of fluids, thereby separating the fluid from the mixture.
  • the membranes of the present invention are useful for a variety of separation processes including, but not limited to, the separation of mixtures of gases, liquids, vapors, aqueous solutions, hydrocarbon isomers, olefins/paraffins, iso/normal paraffins, proteins, as well as recovery and purification of biofuel from acetone-butanol-ethanol (ABE) fermentation (e.g. pervaporation), adsorption, deep sulfurization of gasoline and diesel fuel, desalination of water, and forward osmosis processes.
  • i ne carao-poiyoenzoxazoie copolymers oi me invention are iaoricatea rrom a thermal rearrangement of copolyimide materials.
  • the membranes exhibit high thermal and mechanical stability, may adopt a variety of geometries, and also demonstrate enhanced gas permeability and permselectivity as compared to polybenzoxazole membranes.
  • FIG. 1 shows ATR-RT-IR spectra of membranes obtained in Example 2 and Example 3.
  • FIG. 2 shows ATR-RT-IR spectra of membranes obtained in Example 5 and Example 6.
  • FIG. 4 shows TGA curves of membranes obtained in Example 2 and Example 3.
  • FIG. 5 shows TGA curves of membranes obtained in Example 5 and Example 6.
  • FIG. 7 shows a graph comparing oxygen permeability (Barrer) and oxygen/nitrogen selectivity for membranes prepared in Example 3, Example 6, and Example 9.
  • FIG. 8 shows a graph comparing hydrogen permeability (Barrer) and hydrogen/methane selectivity for membranes prepared in Example 3, Example 6, and Example 9.
  • r i . y snows a grapn companng caroon aioxiae permeaDiniy ana carbon dioxide/methane selectivity for membranes prepared in Example 3, Example 6, and Example 9.
  • novel cardo-polybenzoxazole (CPBO) copolymer membranes have been prepared from a thermal rearrangement of cardo-polyimide (CPI) copolymer membranes.
  • the CPI copolymer membranes are prepared by reacting various compositions of diamine and cardo-diamine starting materials with a substituted diphthalic anhydride, and subsequently casting the resultant material into a membrane.
  • the cardo-polybenzoxazole copolymer membranes of the invention demonstrate good thermal and mechanical stability, and are fabricated into geometries comprising flat sheet, hollow fiber, tube, thin film, and disk.
  • gases that are suitable for use with the invention include, but are not limited to, H 2 , 0 2 , N 2 , CH 4 , and C0 2 .
  • this invention is suitable for the separation of mixtures of gases including, but not limited to, CO2/N2, C0 2 /CH 4 , 0 2 /N 2 , and H 2 /CH 4 .
  • the novel cardo-polybenzoxazole copolymer (CPBOc) membranes of the invention are generated from a thermal rearrangement of cardo-copolyimide (CcPI) membranes.
  • CcPI membranes are cast into a desired geometry from a solution of CcPI in solvent.
  • the synthesis of the cardo-copolyimide polymer, as well as the poiyimide polymer, and the cardopolyimide polymer, is as follows.
  • R l and R 2 are independently (Ci-C 6 )alkyl or (C[-C 6 )haloalkyl;
  • n is an integer ranging from 0 to 1 ;
  • the diphthalic anhydride can be any organicphthalic anhydride.
  • the diphthalic anhydride can be any organicphthalic anhydride.
  • 3,3',4,4'-biphenyltetracarboxylic dianhydride 4,4'-oxydiphthalic anhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, pyromellitic dianhydride, 1 ,4,5,8-naphthalenetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclobutane-l,2,3,4-tetracarboxylic dianhydride, or perylene-3,4,9,10- tetracarboxylic dianhydride, or any other aromatic anhydride known to one of skill in the art, and in a preferred embodiment, the diphthalic anhyridide is 4,4'- hexafluoroisopropylidenediphthalic anhydride (6FDA).
  • 6FDA 4,4'- hexafluoroisopropylidenediphthalic anhydride
  • tne nyaroxyi-containing diamine can oe z -aiaminopnenoi, 2,4- diaminophenol, or 4,4'-methylenebis(2-aminophenol), and in a preferred
  • PI is synthesized with diamine 3,3'- dihydroxybenzidine (HAB).
  • HAB diamine 3,3'- dihydroxybenzidine
  • the synthesis of the PI membranes is carried out in an organic solvent.
  • the solvent is tetrahydrofuran, acetone, dimethylsulfoxide, cyclohexanone, or cyclopentanone.
  • the solvent is an amide solvent, selected from a list comprising NJV- dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylformamide (NMF), formamide, iV-Methyl-2-pyrrolidinone (NMP), or 2-pyrrolidinone.
  • the solvent used in the synthesis of PI is V-Methyl-2- pyrrolidinone (NMP).
  • cardo-polyimide (CPI) was synthesized by polycondensation of a diphthalic anhydride with the formula:
  • R and R are independently (Ci-C )alkyl or (CrC 6 )haloalkyl; with a hydroxyl-containing cardo-diamine of the formula:
  • A is either a methylene linker of the formula CR 3 R 4 or a polycyclic aromatic hydrocarbon such that when A is not present, there is a fused ring system, and when A is present, there is a multi-ring system;
  • R 3 and R 4 are independently (Ci-C )alkyl or (C -C 2 )aryl, or R 3 and R 4 can be taken together to form a cardo group as shown in formula (II);
  • the diphthalic anhydride can be 3, 3 ',4,4'- biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, benzophenone- 3,3',4,4'-tetracarboxylic dianhydride pyromellitic dianhydride, 1,4,5,8- napninaieneteiracarooxync aiannyariae, etnyieneaiammetetraacetic aiannyanae, cyclobutane-l,2,3,4-tetracarboxylic dianhydride, or perylene-3,4,9,10- tetracarboxylic dianhydride, or any other aromatic anhydride known to one of skill in the art, and in a preferred embodiment, the diphthalic anhyridide is 4,4'- hexafiuoroisopropylidenediphthalic anhydride (6FDA).
  • 6FDA 4,4'- hexafiu
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are each CF 3 .
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are taken together to form a cardo group selected from the list comprising phenalene, acenaphthene, benzo[a]fluorene, and fluorene.
  • the aminophenol groups are fused to form a 2-ring bis(amino)bisphenol system comprising 3,6-diaminonaphthalene-2,7-diol.
  • A is present as a polycyclic aromatic hydrocarbon, it is taken together with the aminophenol groups to form a 3-ring bis(amino)bisphenol system, a 4-ring bis(amino)bisphenol system, a 5-ring bis(amino)bisphenol system, or a larger multi- ring bis(amino)bisphenol system.
  • the hydroxyl-containing cardo- diamine is selected from but not limited to diamino-polycyclic aromatic
  • hydrocarbon diols comprising 3,6-diaminoanthracene-2,7-diol, 1 ,8- diaminophenanthrene-2,7-diol, 2,7-diaminophenanthrene-3,6-diol, 3,6- diaminophenanthrene-2,7-diol, 3,8-diaminotetracene-2,9-diol, 1 ,8-diaminopyrene- 2,7-diol, 3,6-diaminotriphenylene-2,7-diol, l ,8-diaminotriphenylene-2,7-diol, 3,8- diaminochrysene-2,9-diol, 3,10-diaminobenzo[c]phenanthrene-4,9-diol, 2,5- diaminoperylene-l ,6-diol, 3,9-aminopentacen
  • CPI is synthesized with cardo-diamine 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BisAHPF).
  • BisAHPF cardo-diamine 9,9-bis(3-amino-4-hydroxyphenyl)fluorene
  • the synthesis of the CPI membranes is carried out in an organic solvent.
  • the solvent is tetrahydrofuran, acetone, dimethylsulfoxide, cycionexanone, or cyclopentanone.
  • the solvent is an amide solvent, selected from a list comprising N,N-dimethylacetamide (DMA), N,iV-dimethylformamide (DMF), N-methylformamide (NMF), formamide, N- Methyl-2-pyrrolidinone (NMP), or 2-pyrrolidinone.
  • the solvent used in the synthesis of CPI is N-Methyl-2-pyrrolidinone (NMP).
  • 3 ⁇ 4uDstituent . is i tor a tnermaiiy lmi ize polymer, or - ⁇ ( ⁇ 3 )U tor a cnemicaiiy imidized polymer [9];
  • n is an integer from 0 to 100.
  • CcPI Cardo-copolyimides
  • R and R are independently (Ci-C )alkyl or (Ci-C 6 )haloalkyl;
  • n is an integer ranging from zero to 1 ;
  • A is either a methylene linker of the formula CR 3 R 4 or a polycyclic aromatic hydrocarbon such that when A is not present, there is a fused ring system, and when A is present, there is a multi-ring system;
  • R 3 and R 4 are independently (Ci-C 6 )alkyl or (C 6 -C 24 )aryl, or R 3 and R 4 can be taken together to form a cardo group;
  • the ratio of hydroxyl-containing diamine to hydroxyl-containing cardo-diamine in the mixture is in the range of 99:1 up to 1 :99 hydroxyl-containing diamine to hydroxyl-containing cardo-diamine.
  • the ratio of hydroxyl-containing diamine to hydroxyl- containing cardo-diamine in the mixture includes, but is not limited to 95:5, 90: 10, 85: 15, 80:20, 70:30, 50:50, and 30:70.
  • the ratio of hydroxyl-containing diamine to hydroxyl-containing cardo- diamine in the mixture to generate the CcPI polymer is 90: 10.
  • the diphthalic anhydride can be 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclobutane- 1 ,2,3 ,4- tetracarboxylic dianhydride, or perylene-3 ,4,9,10-tetracarboxylic dianhydride, or any other aromatic anhydride known to one of skill in the art, and in a preferred embodiment, the diphthalic anhyridide is 4,4'-hexafluoroisopropylidenediphthalic anhydride (6FDA).
  • 6FDA 4,4'-hexafluoroisopropylidenediphthalic anhydr
  • the hydroxyl-containing diamine can be 2,5-diaminophenol, 2,4-diaminophenol, or 4,4'-methylenebis(2- aminophenol), and in a preferred embodiment of the invention, CcPI is synthesized with diamine 3,3'-dihydroxybenzidine (HAB).
  • HAB 3,3'-dihydroxybenzidine
  • R and R 4 in the hydroxyl-containing cardo-diamine are each CF 3 .
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are taken together to form a cardo group selected from the list comprising phenalene, acenaphthene, benzo[a]fluorene, and fluorene.
  • the aminophenol groups are fused to form a 2-ring bis(amino)bisphenol system comprising 3,6-diaminonaphthalene-2,7-diol.
  • A is present as a polycyclic aromatic hydrocarbon, it is taken together with the aminophenol groups to form a 3 -ring bis(amino)bisphenol system, a 4-ring bis(amino)bisphenol system, a 5 -ring bis(amino)bisphenol system, or a larger multi- ring bis(amino)bisphenol system.
  • the hydroxyl-containing cardo- diamine is selected from but not limited to diamino-polycyclic aromatic
  • hydrocarbon diols comprising 3,6-diaminoanthracene-2,7-diol, 1,8- diaminophenanthrene-2,7-diol, 2,7-diaminophenanthrene-3,6-diol, 3,6- diaminophenanthrene-2,7-diol, 3,8-diaminotetracene-2,9-diol, 1 ,8-diaminopyrene- -., ⁇ -diol, 3,b-diaminotnphenylene- , /-diol, l,8-diaminotriphenylene-2, /-dioI, 3,8- diaminochrysene-2,9-diol, 3,10-diaminobenzo[c]phenanthrene-4,9-diol, 2,5- diaminoperylene-l,6-diol, 3,9-aminopentace
  • CcPI is synthesized with cardo-diamine 9,9-bis(3-amino-4-hydroxyphenyl)iluorene (BisAHPF).
  • BisAHPF cardo-diamine 9,9-bis(3-amino-4-hydroxyphenyl)iluorene
  • the synthesis of the CcPI membranes is carried out in an organic solvent.
  • the solvent is tetrahydrofuran, acetone, dimethylsulfoxide, cyclohexanone, or cyclopentanone.
  • the solvent is an amide solvent, selected from a list comprising N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylformamide (NMF), formamide, N- Methyl-2-pyrrolidinone (NMP), or 2-pyrrolidinone.
  • the solvent used in the synthesis of CcPI is N-Methyl-2-pyrrolidinone (NMP).
  • Substituent R is H for a thermally imidized polymer, or -C(CH 3 )0 for a chemically imidized polymer [9];
  • n and n are each integers ranging from 0 to 100, wherein the sum of m and n is 100.
  • m and n are integers from 5 to 95, wherein the sum of m and n is 100, and in a preferred embodiment of the invention, m and n are integers from 10 to 90, wherein the sum of m and n is 100.
  • the cardo-copolyimides of the invention are random copolymers.
  • the polyimide (PI), cardopolyimide (CPI), and cardo-copolyimide (CcPI) membranes of the invention are made by a process that comprises a) preparing a solution of PI, CPI, or CcPI in solvent, b) fabricating the solution to produce a membrane, and c) drying the membrane.
  • the membranes of PI, CPI, or CcPI can be fabricated into flat sheet, hollow fiber, tube, thin film, and disk geometries.
  • the PI, CPI, and CcPI membranes of the invention are manufactured by the methods described below, which are not intended to be limiting in any way.
  • the solution of PI, CPI, or CcPI is created in an organic solvent capable of fully solvating the polymer.
  • the organic solvent capable of fully solvating the polymer.
  • the solvent is selected from a group comprising acetone, leiranyuroiuran, aimeinyi suiioxiue, cycionexanone, anu cyciopenianone.
  • the solvent used is an amide solvent such as N,N- dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylformamide (NMF), formamide, N-Methyl-2-pyrrolidinone (NMP), or 2-pyrrolidinone.
  • the solvent used to create a solution of PI, CPI, or CcPI is N,N-dimethylformamide (DMF).
  • the PI, CPI, or CcPI solution can be cast onto a form having a desired shape or configuration depending upon the intended end use.
  • the flat sheet is created by first casting the homogeneous solution described in step a) onto a substrate, mold, or form.
  • the substrate, mold, or form is then placed in an oven and dried overnight at a temperature of about 80 °C to evaporate the latent solvent.
  • the pristine PI, CPI, or CcPI membranes are then detached from the substrate, mold, or form and placed into the vacuum oven for complete solvent evaporation by heating from about 75 °C to about 200 °C with a temperature ramping rate of about 25 °C/h.
  • the solution is cast in the form of hollow fibers.
  • the hollow fibers can be fabricated by a non-solvent induced phase inversion method.
  • the inner layer dope and outer layer dope are co-extruded together through a triple-orifice spinneret by a dry-jet/wet spinning process. The detailed description of the set up for dual-layer hollow fiber spinning and process can be found elsewhere [16].
  • the polybenzoxazole (PBO), cardopolybenzoxazole (CPBO), and cardopolybenzoxazole copolymer (CPBOc) membranes of the invention are made by a process that comprises a) providing PI, CPI, or CcPI membranes as described above, and b) subjecting the membranes to thermal treatment at elevated
  • the PBO, CPBO, and CPBOc membranes are manufactured by the methods described below, which are not intended to be limiting in any way.
  • the PI, CPI, or CcPI membranes are subjected to temperature conditions capable of bringing about a thermal rearrangement, in which the array of atoms in the polyimide changes to form a polybenzoxazole.
  • the membranes are subjected ⁇ inermai treatment ax a temperature m me range oi aooui JJU to aooui DU for about 30 minutes to about 60 minutes.
  • the pristine PI, CPI, or CcPI membranes are subjected to thermal treatment at about 425 °C for about 30 minutes under vacuum in a preheated furnace.
  • the membrane is removed from the furnace after the thermal treatment and stored in a desiccator before use.
  • PBO membrane is created by a thermal rearrangement of PI membrane, in which the array of atoms in PI changes to form PBO. This process is depicted below
  • R 1 and R 2 are independently (C]-C 6 )alkyl or (Ci-C 6 )haloalkyl;
  • n is an integer ranging from 0 to 1 ;
  • n is an integer from 0 to 100.
  • CR'R 2 can be deleted, or replaced by oxygen.
  • R 1 and R 2 are each CF 3 .
  • n is zero.
  • Cardopolybenzoxazole (CPBO) membrane is made by a thermal
  • R 1 and R 2 are independently (CrC 6 )alkyl or (Ci-C 6 )haloalkyl;
  • A is either a methylene linker of the formula CR 3 R 4 or a polycyclic aromatic hydrocarbon such that when A is not present, there is a fused ring system, and when A is present, there is a multi-ring system;
  • R 3 and R 4 are independently (d-C 6 )alkyl or (C 6 -C 24 )aryl, or R 3 and R 4 can be taken together to form a cardo group;
  • n is an integer from 0 to 100.
  • CR'R 2 can be deleted, or replaced by oxygen.
  • R 1 and R 2 are each CF 3 .
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are each CF 3 .
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are taken together to form a cardo group selected from the list comprising phenalene, acenaphthene, benzo[a]fluorene, and fluorene.
  • R 3 and R 4 are taken together to be a fluorenyl group.
  • the bis(polybenzoxazole) ring system is fused to 2- ring polybenzoxazole system.
  • the ring-count for the bis(amino)bisphenol reactants is adhered to in assigning the ring-count for the polybenzoxazole system.
  • the ring system is fused to form a polybenzoxazole with a naphthalene hydrocarbon core, as shown in an example embodiment, below.
  • wnen A IS present as a poiycyciic aromatic nyarocarDon, it is taken together with the polybenzoxazole groups to form a 3 -ring polybenzoxazole system, a 4-ring polybenzoxazole system, a 5 -ring polybenzoxazole system, or a larger multi-ring polybenzoxazole system.
  • the aromatic hydrocarbon core of the diamino-polycyclic aromatic hydrocarbon diol is selected from a list of poiycyciic aromatic hydrocarbons comprising anthracene, phenanthrene, tetracene, pyrene, triphenylene, chrysene, benzo[c]phenanthrene, perylene, and pentacene, or any other poiycyciic aromatic hydrocarbon known to one of skill in the art.
  • a preferred embodiment of A is:
  • substituent R is H or -C(CH 3 )0;
  • n is an integer from 0 to 100.
  • Cardopolybenzoxazole copolymer (CPBOc) membrane is made through a thermal rearrangement of CcPI membrane, as depicted below:
  • R 1 and R 2 are independently (Ci-C 6 )alkyl or (C]-C 6 )haloalkyl;
  • A is either a methylene linker of the formula CR 3 R 4 or a polycyclic aromatic hydrocarbon such that when A is not present, there is a fused ring system, and when A is present, there is a multi-ring system;
  • R 3 and R 4 are independently (Q-C ⁇ alkyl or (C 6 -C 2 4)aryl, or R 3 and R 4 can be taken together to form a cardo group;
  • p is an integer ranging from zero to 1 ;
  • n is an integer ranging from 0 to 100;
  • n is an integer from 0 to 100;
  • m and n are integers from 5 to 95, wherein the sum of m and n is 100, and in a preferred embodiment of the invention, m and n are integers from 10 to 90, wherein the sum of m and n is 100.
  • the cardo-polybenzoxazole copolymers of the invention are random copolymers.
  • CR R can be deleted, or replaced by oxygen.
  • R 1 and R 2 are each CF 3 .
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are each CF 3 .
  • R 3 and R 4 in the hydroxyl-containing cardo-diamine are taken together to form a cardo group selected from the list comprising phenalene, acenaphthene, benzo[a]fluorene, and fluorene.
  • R 3 and R 4 are taken together to be a fluorenyl group.
  • the bis(polybenzoxazole) nng system is fused to 2- ring polybenzoxazole system.
  • the ring-count for the bis(amino)bisphenol reactants is adhered to in assigning the ring-count for the polybenzoxazole system.
  • the ring system is fused to form a polybenzoxazole with a naphthalene hydrocarbon core, as shown in an example embodiment, below.
  • A is present as a polycyclic aromatic hydrocarbon, it is taken together with the polybenzoxazole groups to form a 3 -ring polybenzoxazole system, a 4-ring polybenzoxazole system, a 5-ring polybenzoxazole system, or a larger multi-ring polybenzoxazole system.
  • the aromatic hydrocarbon core of the diamino-polycyclic aromatic hydrocarbon diol is selected from a list of polycyclic aromatic hydrocarbons comprising anthracene, phenanthrene, tetracene, pyrene, triphenylene, chrysene, benzo[c]phenanthrene, perylene, and pentacene, or any other polycyclic aromatic hydrocarbon known to one of skill in the art.
  • bubstituent K is i or - ( i-i 3 )U depending upon the method ot lmidization; and m and n are each integers ranging from 0 to 100, wherein the sum of m and n is 100.
  • m and n are integers from 5 to 95, wherein the sum of m and n is 100, and in a preferred embodiment of the invention, m and n are integers from 10 to 90, wherein the sum of m and n is 100.
  • the cardo-polybenzoxazole copolymers of the invention are random copolymers.
  • the cardopolybenzoxazole copolymers of the invention are suitable for the separation of fluids in a variety of processes, including, but not limited to, the separation of mixtures of gases, liquids, vapors, aqueous solutions, hydrocarbon isomers, olefins/paraffins, iso/normal paraffins, proteins, as well as recovery and purification of biofuel from acetone-butanol-ethanol (ABE) fermentation ⁇ e.g.
  • One example separation process that is particularly suitable for use with the invention is the separation of at least one gas from a mixture of gases.
  • This invention is even more particularly suitable for use in the separation of gaseous mixtures comprising C0 2 /N 2 , C0 2 /CH 4 , 0 2 N 2 , and H 2 /CH 4 .
  • the detailed experimental procedure and equipment design for pure gas permeation measurement is reported elsewhere [17].
  • the pure gas permeability is measured by using a constant volume method. Gas permeation experiments may employ a diffusion cell, which is separated into two compartments by a membrane of the present invention.
  • the upstream feed pressure and testing temperature are maintained at a constant level, and the increase in downstream pressure is measured once the system reaches a steady state. From this measurement, the permeability and selectivity values are obtained.
  • the cardo-polybenzoxazole copolymer membrane materials of the invention are particularly advantageous in their application to separation technologies. As compared to known examples of polybenzoxazole membranes, the materials of the present invention exniDit supenor perrormance in gas permeaointy ana separation processes, surpassing Robeson's upper bound trade-off curves [6].
  • Alkyl means a saturated aliphatic branched or straight-chain hydrocarbon radical having the specified number of carbon atoms that can be substituted or unsubstituted.
  • (Ci-C 6 ) alkyl means a radical having from 1- 6 carbon atoms in a linear or branched arrangement.
  • (Ci-C 6 )alkyl includes methyl, ethyl, propyl, butyl, pentyl and hexyl.
  • Substituted alkyl includes alkyl groups, as defined above, in which one or more hydrogens is replaced by an alkoxy, amino, hydroxyl, or thiol group.
  • Haloalkyl includes mono, poly, and perhaloalkyl groups, where “alkyl” is defined above, and where each halogen is independently selected from fluorine, chlorine, and bromine.
  • (C6-C 24 )aryl means carbocyclic aromatic rings.
  • Carbocyclic aromatic group may be used interchangeably with the terms “aryl,” “aryl ring,” “carbocyclic aromatic ring,” “aryl group,” and “carbocyclic aromatic group.”
  • a "substituted aryl group” is substituted at any one or more substitutable ring atom.
  • R 3 and R 4 can be a monocyclic, bicyclic, or tricyclic carbocyclic ring system containing from 6 to 24 carbon atoms that can include phenyl (Ph), naphthyl, anthracenyl, 1 ,2-dihydronaphthyl, 1 ,2,3,4-tetrahydronaphthyl, indanyl, indenyl, and in a preferred embodiment, R 3 and R 4 are taken together to be fluorenyl.
  • cardo group means a sterically large polycyclic aromatic group.
  • the cardo group is fluorenyl, anthracenyl, napthyl, phenalenyl, acenaphthenyl, benzo[a]fluorenyl, and in a more preferred embodiment, the cardo group is fluorenyl.
  • Polyimide (PI) was synthesized using 4,4'- hexafluoroisopropylidenediphthalic anhydride (6FDA) and 3,3'-dihydroxybenzidine (HAB): 5 mmol HAB was dissolved in 13.2 g NMP in a 50 mL conical flask equipped with nitrogen or argon inlet. After stirring under nitrogen or argon atmosphere for 1 h, 5 mmol 6FDA was added into the solution and continuously stirred at least 3 h in an ice bath. The intermediate poly(amic acid) was then chemically imidized to polyimide using acetic anhydride as catalyst and pyridine as weak base.
  • 6FDA 4,4'- hexafluoroisopropylidenediphthalic anhydride
  • HAB 3,3'-dihydroxybenzidine
  • the PI (6FDA-HAB) membrane was prepared as follows: 0.5 g of the polymer synthesized in Example 1 was dissolved in 9.5 g NN-dimethylformamide (DMF) under stirring for 2 h to obtain a homogeneous casting solution. The homogeneous solution was casted onto a petri dish and dried in an oven at 80 °C overnight to evaporate the latent solvent. The pristine membranes were then detached from the petri dish and placed into a vacuum oven for complete solvent evaporation by heating from 75 °C to 200 °C with a temperature ramping rate of 25 °C/h.
  • Example 3 Preparation of Polybenzoxazole Polymer Membrane (PBO) from PI (6FDA-HAB) at 425 °C
  • the polybenzoxazole polymer membrane, PBO (6FDA-HAB), was prepared by thermally treating the PI (6FDA-HAB) membrane prepared in Example 2 in a preheated furnace at 425 °C under vacuum for 30 minutes.
  • Example 4 Synthesis of Car do-containing Polyimide (CP I) from 4,4'- hexafluoroisopropyl- idenediphthalic anhydride (6FDA) and 9,9-bis(3-amino-4- hydroxyphenyl)fluorene (BisAHPF)
  • Cardo-containing polyimide (CPI) was synthesized using 4,4'- hexafluoroisopropylidenediphthalic anhydride (6FDA) and 9,9-bis(3-amino-4- hydroxyphenyl)fluorene (BisAHPF). 5 mmol BisAHPF was dissolved in 16.5 g NMP in a 50 mL conical flask equipped with a nitrogen or argon inlet. After stirring under nitrogen or argon atmosphere for 1 h, 5 mmol 6FDA was added into the solution and continuously stirred at least 3 h in an ice bath.
  • 6FDA 4,4'- hexafluoroisopropylidenediphthalic anhydride
  • BisAHPF 9,9-bis(3-amino-4- hydroxyphenyl)fluorene
  • the intermediate cardo- containing poly(amic acid) was then chemically imidized to cardo-containing polyimide using acetic anhydride as catalyst and pyridine as weak base. 21.2 mmol acetic anhydride and 25.8 mmol of pyridine were added into the cardo-containing poly(amic acid) and the solution was stirred at room temperature at least 12 h. The resulted cardo-containing polyimide solution was precipitated into 1000 mL methanol under stirring. After washing with methanol three times, the polymer was dried in a vacuum oven at 60 °C overnight, and stored in a desiccator before use.
  • the CPI (6FDA-BisAHPF) membrane was prepared as follows: 0.5 g of the polymer synthesized in Example 4 was dissolved in 9.5 g DMF under stirring for 2 h to obtain a homogeneous casting solution. The homogeneous solution was casted onto a petri dish and dried in an oven 80 °C overnight to evaporate the latent solvent. The pristine membranes were then detached from the petri dish and placed into the vacuum oven lor complete solvent evaporation by heating Irom 75 U to 200 °C with a temperature ramping rate of 25 °C/h.
  • Example 7 Synthesis of Car do-containing Copolyimide (CcPI) from
  • Cardo-containing copolyimides were synthesized using 4,4'- hexafluoroisopropylidenediphthalic anhydride (6FDA), 3,3'-dihydroxybenzidine (HAB), and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BisAHPF).
  • 6FDA 4,4'- hexafluoroisopropylidenediphthalic anhydride
  • HAB 3,3'-dihydroxybenzidine
  • BisAHPF 9,9-bis(3-amino-4-hydroxyphenyl)fluorene
  • cardo-containing copolyimide with molar ratio of HAB:BisAHPF of 95:5, 4.75 mmol HAB and 0.25 mmol BisAHPF were dissolved in 13.4 g NMP in a 50 mL conical flask equipped with nitrogen or argon inlet. After stirring under nitrogen or argon atmosphere for 1 h, 5 mmol 6FDA was added into the solution and continuously stirred at least 3 h in an ice bath. The intermediate cardo-containing poly(co-amic acid) was then chemically imidized to cardo-containing copolyimide using acetic anhydride as catalyst and pyridine as weak base.
  • the CcPI (6FDA-HAB(m)-BisAHPF(n)) membranes were prepared as follows: 0.5 g of copolymer synthesized in Example 7 was dissolved in 9.5 g DMF under stirring for 2 h to obtain a homogeneous casting solution. The homogeneous solution was casted onto a petri dish and dried in an oven at temperature of 80 °C overnight to evaporate the latent solvent. The pristine copolymer membranes were then detached from the petri dish and placed into the vacuum oven for complete solvent evaporation by heating from 75 °C to 200 °C with a temperature ramping rate of 25 °C/h.
  • Example 10 Attenuated Total Reflectance - Fourier-transformed Infra-red (ATR- FTIR)
  • Cardo-containing polyimide (CPI) of Example 5 shows the characteristic IR stretch of an imide group at 1099 cm “1 , 1381 cm “1 , 1720 cm “1 and 1782 cm “1 .
  • the characteristic stretches at 1058 cm “1 , 1480 cm “1 , 1550 cm “1 and 1617 cm “1 were observed for the CPBO membrane of Example 6.
  • 6FDA-HAB(90)- BisAHPF(lO) of Example 9 shows the characteristic IR stretches of an imide group at 1099 cm “1 , 1381 cm “1 , 1720 cm “1 and 1782 cm “1 .
  • Example 8 was converted to polybenzoxazole membrane obtained in Example 9 by thermal treatment.
  • FIG. 4 shows the TGA curves of PI of Example 2 and PBO of Example 3. It can be seen from the figure that the polyimide of Example 2 starts to thermally rearrange in the temperature range of 300 to 500 °C, whereas thermal degradation of the polybenzoxazole of Example 3 is not observed within this thermal conversion temperature.
  • TGA curves of CPI of Example 5 and CPBO of Example 6 is shown in FIG. 5. It can be seen from the figure that the cardo-containing polyimide of Example 5 — starts to thermally rearrange in the temperature range from 300 to 500 °C, whereas thermal degradation of the polybenzoxazole of Example 6 is not observed within this thermal conversion temperature.
  • Example 3 is not observed within this thermal conversion temperature.
  • Example 12 Pure Gas Permeation Results of Polybenzoxazole Polymer (PBO), Cardo-polybenzoxazole polymer (CPBO) and Cardo-polybenzoxazole
  • the detailed experimental procedure and equipment design for pure gas permeation measurement is reported elsewhere [17].
  • the pure gas permeability was measured by using a constant volume method.
  • the feed pressure and testing temperature is maintained at j.-> atm ana respectively, ine gases were measured in the sequence of H 2 , 0 2 , N 2 , CH 4 , and C0 2 and each reported value is the average of three experimental data points.
  • the gas permeability was determined from the rate of downstream pressure increase (dp/dt) obtained using the following equation:
  • D represent average effective diffusivity (cm 2 /s)
  • S apparent sorption coefficient/solubility (cm 3 (STP)/cm 3 polymer cm Hg).
  • V is volume of the downstream chamber (cm 3 )
  • L is film thickness (cm)
  • A represents effective area of the membrane (cm )
  • T is experimental temperature (K)
  • p 2 represents pressure of the feed gas in the upstream chamber (psia).
  • polybenzoxazole PBO
  • cardo-polybenzoxazole CPBO
  • the CPBOc of 6FDA-HAB(90)-BisAHPF(10) shows the highest permeability for all gases, with moderate 0 2 2 , H 2 /CH 4 , and C0 2 /CH 4 selectivities.
  • lable l Fure gas permeation results ot polybenzoxazole (FBU , cardo- polybenzoxazole (CPBO) and cardo-polybenzoxazole copolymer (CPBOc) membranes
  • FIGs. 7 to 9 are the graphs comparing oxygen permeability (Barrer) and oxygen/nitrogen selectivity, hydrogen permeability (Barrer) and hydrogen/methane selectivity and carbon dioxide permeability (Barrer) and carbon dioxide/methane selectivity for all membranes prepared in Examples 3, 6 and 9.
  • the materials of the present invention showed superior gas permeabilities with moderate selectivities, surpassing Robeson's upper bound trade-off curves [6].
  • H. B. Park, et al. Polymers with cavities tuned for fast selective transport of small molecules and ions, Science, 318 (2007) 254-258.

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Abstract

Cette invention concerne une série de membranes en copolymère de cardo-polybenzoxazole, des procédés pour les préparer par réarrangement thermique de membranes de cardo-copolyimide, et des procédés pour séparer un fluide d'un mélange de fluides à l'aide de ladite membrane en copolymère de cardo-polybenzoxazole.
PCT/SG2012/000153 2011-04-29 2012-04-27 Membranes en polymère/copolymère de cardo-polybenzoxazole pour une perméabilité améliorée et son procédé de fabrication Ceased WO2012148360A1 (fr)

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WO2017130604A1 (fr) * 2016-01-29 2017-08-03 富士フイルム株式会社 Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, et procédé de séparation de gaz
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